Lithium transference in electrolytes with star-shaped multivalent anions measured by electrophoretic NMR.

One approach for improving lithium transference in electrolytes is through the use of bulky multivalent anions. We have studied a multivalent salt containing a bulky star-shaped anion with a polyhedral oligomeric silsesquioxane (POSS) center and lithium counterions dissolved in a solvent. The charge on each anion, z-, is equal to -20. The self-diffusion coefficients of all species were measured by pulsed field gradient NMR (PFG-NMR). As expected, anion diffusion was significantly slower than cation diffusion. An approximate transference number, also referred to as the current fraction (measured by Bruce, Vincent and Watanabe method), was higher than those expected from PFG-NMR. However, the rigorously defined cation transference number with respect to the solvent velocity measured by electrophoretic NMR was negative at all salt concentrations. In contrast, the approximate transference numbers based on PFG-NMR and current fractions are always positive, as expected. The discrepancy between these three independent approaches for characterizing lithium transference suggests the presence of complex cation-anion interactions in solution. It is evident that the slow self-diffusion of bulky multivalent anions does not necessarily lead to an improvement of lithium transference.

Surface-Functionalized Polystyrene Latexes Using Itaconate-Based Surfmers.

Itaconic acid was readily transformed to a series of amphiphilic diesters via stepwise esterification of itaconic anhydride; the diesters carry one alkyl (cetyl or octyl) group and either a PEG, glyceryl, or dopamine segment. These diesters were used as surfmers for the preparation of polystyrene (PS) emulsions, with the expectation that the surface of the emulsion particles would carry PEG, glyceryl or dopamine units. NMR spectroscopic studies revealed that the surfmers were covalently incorporated into the polystyrene chains; furthermore, NMR tube polymerization experiments also confirmed that when the PEG surfmer was used, the PEG segments are indeed present on the surface of the emulsion particles. The size of the PEGlyated PS emulsions was readily varied from 35 to 140 nm by changing the mole fraction of surfmer used. In the case of the glyceryl and dopamine carrying surfmers, an octyl unit was used as the hydrophobic segment to ensure appropriate hydrophobic-hydrophilic balance; it was noticed that significantly larger mole fractions of the surfmers were required (15-20 mol %) to generate stable emulsions with particle sizes of about 150 nm. The PS emulsions carrying dopamine units on the surface were found to adhere to glass surfaces; thus suggesting that such "sticky" emulsion particles could be used to functionalize different types of surfaces. Finally, itaconate diesters bearing cetyl and perfluorooctyl segments were also prepared and shown to copolymerize with styrene to generate fluoroalkyl-enriched PS copolymers; these were used to generate hydrophobic coatings, with water contact angles of over 120°. Thus, itaconate-based surfmers are readily accessible alternatives for the preparation of emulsions with tailored size and surface functionality.

Molecular Origin of High Cation Transference in Mixtures of Poly(pentyl malonate) and Lithium Salt.

The rational development of new electrolytes for lithium batteries rests on the molecular-level understanding of ion transport. We use molecular dynamics simulations to study the differences between a recently developed promising polymer electrolyte based on poly(pentyl malonate) (PPM) and the well-established poly(ethylene oxide) (PEO) electrolyte; LiTFSI is the salt used in both electrolytes. Cation transference is calculated by tracking the correlated motion of different species. The PEO solvation cage primarily contains 1 chain, resulting in strong correlations between Li+ and the polymer. In contrast, the PPM solvation cage contains multiple chains, resulting in weak correlations between Li+ and the polymer. This difference results in a high cation transference in PPM relative to PEO. Our comparative study suggests possible designs of polymer electrolytes with ion transport properties better than both PPM and PEO. The solvation cage of such a hypothetical polymer electrolyte is proposed based on insights from our simulations.

Ion Solvation Cage Structure in Polymer Electrolytes Determined by Combining X-ray Scattering and Simulations.

Solvation structure plays a crucial role in determining ion transport in electrolytes. We combine wide-angle X-ray scattering (WAXS) and molecular dynamics (MD) simulation to identify the solvation cage structure in two polymer electrolytes, poly(pentyl malonate) (PPM) and poly(ethylene oxide) (PEO) mixed with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. As the salt concentration increases, the amorphous halo in the pure polymers is augmented by an additional peak at low scattering angles. The location of this peak and its height are, however, different in the two electrolytes. By decoupling the total intensity into species contributions and mapping scattering peaks to position-space molecular correlations, we elucidate distinct origins of the additional peak. In PPM, it arises from long-range charge-ordering between solvation cages and anions, while in PEO it is dominated by correlations between anions surrounding the same cage. TFSI- ions are present in the PPM solvation cage, but expelled from the PEO solvation cage.

Cycling of block copolymer composites with lithium-conducting ceramic nanoparticles.

Solid polymer and perovskite-type ceramic electrolytes have both shown promise in advancing solid-state lithium metal batteries. Despite their favorable interfacial stability against lithium metal, polymer electrolytes face issues due to their low ionic conductivity and poor mechanical strength. Highly conductive and mechanically robust ceramics, on the other hand, cannot physically remain in contact with redox-active particles that expand and contract during charge-discharge cycles unless excessive pressures are used. To overcome the disadvantages of each material, polymer-ceramic composites can be formed; however, depletion interactions will always lead to aggregation of the ceramic particles if a homopolymer above its melting temperature is used. In this study, we incorporate Li0.33La0.56TiO3 (LLTO) nanoparticles into a block copolymer, polystyrene-b-poly (ethylene oxide) (SEO), to develop a polymer-composite electrolyte (SEO-LLTO). TEMs of the same nanoparticles in polyethylene oxide (PEO) show highly aggregated particles whereas a significant fraction of the nanoparticles are dispersed within the PEO-rich lamellae of the SEO-LLTO electrolyte. We use synchrotron hard x-ray microtomography to study the cell failure and interfacial stability of SEO-LLTO in cycled lithium-lithium symmetric cells. Three-dimensional tomograms reveal the formation of large globular lithium structures in the vicinity of the LLTO aggregates. Encasing the SEO-LLTO between layers of SEO to form a "sandwich" electrolyte, we prevent direct contact of LLTO with lithium metal, which allows for the passage of seven-fold higher current densities without signatures of lithium deposition around LLTO. We posit that eliminating particle clustering and direct contact of LLTO and lithium metal through dry processing techniques is crucial to enabling composite electrolytes.

A scalable and tunable thermoreversible polymer for 3D human pluripotent stem cell biomanufacturing.

Human pluripotent stem cells (hPSCs) are an exciting and promising source to enable cell replacement therapies for a variety of unmet medical needs. Though hPSCs can be successfully derived into numerous physiologically relevant cell types, effective translation to the clinic is limited by challenges in scalable production of high-quality cells, cellular immaturity following the differentiation process, and the use of animal-derived components in culture. To address these limitations, we have developed a fully defined, reproducible, and tunable thermoreversible polymer for high-quality, scalable 3D cell production. Our reproducible synthesis method enables precise control of gelation temperature (24°C-32°C), hydrogel stiffness (100-4000 Pa), and the prevention of any unintended covalent crosslinking. After material optimization, we demonstrated hPSC expansion, pluripotency maintenance, and differentiation into numerous lineages within the hydrogel. Overall, this 3D thermoreversible hydrogel platform has broad applications in scalable, high-quality cell production to overcome the biomanufacturing burden of stem cell therapy.